Polymeric compositions



Patented June 27, 1950 ,James -.Wtherspoon Fisher-,Harold ,Bates,,;andEdward l-wiuiam Wheatley, .Snond n, near ,Derby,,England, assignors 'toCelanese flopperation of America, a corporation ofjDelaware ZNoiDrawing.Application July 2, 1948, sci-farm).

3&818. ln'fireat BritainAugust 12,119,4 7

This invention relates .to improvements in .mlymericmaterials.

It .is wellLknown that. a number of, ,fibreeform 'ing or fihn-formingpolymers, lforrexample cellulose acetate, cellulose .aceto-butyrate,cellulose butyrate, cellulose .aceto-stearate, ethylcellulose,..oxyethyl -cellulose, oxyethyl vcellulose acetate,"benzylcellulose and various other cellulose derivatives, various polyvinylcompounds such as polyvinyl chloride-acetate, polymethyl meth- -acrylateand -polymethyl acrylate, have little or no affinity for acid woolcolours buthavea good affinity :for-the dispersediinsoluble 1 type ofdyestuff, now generally applied to celluloseacetate.

U..S.,application S. No...6(l9,031 filed .August 4, 1945 describes theproduction of nitrogencontaining polymers from dihydrozides ofdicarboxylic acids in presence of hydrazine, e. g. 10% by weight of thedihydrazide, over and above that combined in the dihydrazide and alsodescribes using dicarboxylic esters with an amount of hydrazine inexcess of two moles for each mole of dicarboxylic ester. U. S.application S. No. 662,628 filed April 16, 1946 describes the productionof such polymers from hydrazine and the dicarboxylic acids themselves ortheir anhydrides, again using more than two moles of hydrazine. Polymersmay be produced according to the processes of the specifications whichpossess characteristics, including resistance to degenerative hydrolysisby boiling hydrochloric acid, indicating that they contain the 4-amino-1.2.4-triazo1e nucleus repeated along the main polymer chain. Thesepolymers will be referred to in the present specification aspoly-4-amino- 1.2.4-triazoles.

As described in the said specifications, the polymeric materials may beof sufliciently high molecular weight to render them capable of beingformed into films, filaments or like products, for example by meltspinning or by wet or dry spinning processes.

In U. S. application S. No. 784,306 filed November 5, 1947, we havedescribed processes for acylating the polyaminotriazoles, includingtreatments with acetylating agents or with formic acid reacted, forexample, at water-bath temperature. According to the present invention,filaments, films and the like are made from compositions comprising botha saponifiable cellulose ester which has little or no aflinity for acidwool colours and a poly-4-aminotriazole acylated with a mono-functionalacylating agent.

The filaments, films and like materials may be made from a solution in acommon solvent of the-two types of polymer. In some cases, it may befoundthat the two types of polymer are not .bothsoluble in arsolvent. ofthe ,type which it is .desired-toruse n w 0 rvsp s pr e sInsuoh-la-case.thertwo types. ofpolymer, for example ,cellulose acetateand acylated poly-4- amino-1.2.4-triazole may be dissolved in a com-.monhsolvent, the solutionprecipitated and then .the pre ipitat ta en:up n th desired solvent.

.Tllus, ,for example, cellulose acetatemay firstbe dissolved in coldformic acid, separatelya ,poly- .4-lamino-,-\1.2.4=triazole .isdissolved. in .hot formic .aoid,thetwo;solutions'are,.thenmixedandpoured .in plexcess water- ..cipitated and washed, my .then1bedissolved in .The mixed p ym rs p acetone to form a, viscous emulsifieddope which can quite readily be filtered and used for dry spinninoperations.

The acylated polytriazoles do not themselves confer upon the celluloseacetate or other saponifiable cellulose ester an affinity for acid woolcolours or do not confer a high affinity. Nevertheless, filaments orother materials made from the two types of polymer can be after-treatedwith caustic soda-or other hydrolysing agent, so as to produce filamentswhich have a good afiinity for acid wool colours. The treatment maysaponify the cellulose ester sufficiently toyield a product which'has anafilnity for direct cotton colours and vat colours as well as for theacid wool colours, and moreover, if the saponification of the celluloseester is only partial, affinity for the dispersed insoluble dyestuffsmay be retained.

The following example illustrates the invention:

10 parts by weight of cellulose acetate linters were dissolved in coldformic acid and to this solution was added another solution made bydissolving 1 part of polyl-amino-octamethylene-l.2.4-triazole (fromsebacic dihydrazide and hydrazine as described in U. S. application S.No. 609,031) in hot formic acid and refluxing a described in U. S.application S. No. 784,306. The solutions were then well stirredtogether and poured into excess water. The polymers were precipitated asa white fibrous mass which was thoroughly washed and dried. The productwas then dissolved in 38 parts of acetone to give a dope which was ofeven consistency and which filtered unchanged. The dope was then spun byordinary dry spinning methods. The resulting yarn was immersed in 4%aqueous caustic soda for 3 minutes at 50-60 C. and carefully rinsed freefrom alkali. It showed a good affinity for c F v 2,512,630 1.11. l

acid wool colours, such as Naphthalene Scarlet BS, Azo Geranine 2G8,Brilliant Acid Blue R, Solway Green GS and A20 Acid Black BBL; for thedispersed insoluble type of dyestuii normally applied to celluloseacetate; for the soluble colours which normally have affinity forcellulose acetate, such as Solacet Fast Scarlet BS and Solway Ultra BlueBS; and for cotton colours, such a Sky Blue FF.

Other hydrolysing agents which may be used instead of caustic sodainclude caustic potash, tri-sodium phosphate and strong organic basessuch as methylamine, ethylene diamine, and the quaternary ammoniumhydroxides.

Having described our invention, what we desire to secure by LettersPatent is:

1. Articles comprising essentially a monocarboxylic acid ester ofcellulose which is saponifiable by alkaline reagents and containing apolymer having in its structural unit an acylated 4- amino-LZA-triazolegroup, the acylgroup of which is that of a monocarboxylic acid.

2. Articles comprising essentially cellulose acetate and containing apolymer having in its structural unit an acylated 4-amino-L2a4-triazolegroup, the acyl group of which is that of a monocarboxylic acid.

3. Articles comprising essentially cellulose acetate and containing apolymer having in its structural unit a formylated4-amino-l.2.4-triazole group.

4. Process for the manufacture of products having an affinity for acidwool colors, which comprises saponifying by means of alkaline reagentsarticles comprising essentially a'monocar- 4 boxylic acid ester ofcellulose which is saponifiable by alkaline reagents and containing apolymer having in its structural unit an acylated 4-amino-l.2.4-triazolegroup, the acyl group of which is that of a monocarboxylic acid.

5. Process for the manufacture of products having an affinity for acidwool" colors, which comprise sa-ponifying by means of alkaline reagentsarticles comprising essentially cellulose acetate and containing apolymer having in its structural unit an acylated 4-amino-1.2.4-triazolegroup, the acyl group of which is that of a monocarboxylic acid.

6. Process for the manufacture of products having an afiinity for acidwool colors, which comprises saponifying with alkaline reagents articlescomprising essentially cellulose acetate and containing a polymer havingin its structural unit an acylated 4-amino-l.2.4-triazole group, the

acyl group of which is that of a monocarboxylic acid, saidsaponification being tpartialfso as to confer an affinity for cottoncolorsbutfinsufficient to remove afllnity for the dispersed insolublecellulose acetate colors.

JAMES WOTHERSPOON'FISHIER. HAROLD BATES. EDWARD WILLIAM WHEATLEY.

Number

1. ARTICLES COMPRISING ESSENTIALLY A MONOCARBOXYLIC ACID ESTER OF CELLULOSE WHICH IS SAPONIFIABLE BY ALKALINE REAGENTS AND CONTAINING A POLYMER HAVING IN ITS STRUCTURAL UNIT A ACYLATED 4AMINO-1.2.4-TRIAZOLE GROUPS, THE ACYL GROUP OF WHICH IS THAT OF A MONOCRABOXYLIC ACID. 